Pyrrolidonyl-containing polyesters and polyamides

ABSTRACT

Pyrrolidonyl-containing polyesters and polyamides I to III ##STR1## where R, X, A and Z are defined herein, are suitable as film formers and conditioners in hair-cosmetic formulations, for stabilizing hydrogen-peroxide in aqueous solution, for complexing iodine, as tablet binders and as a constituent of film coatings in pharmaceutical preparations, for enzyme and bleach stabilization in detergent formulations, as an auxiliary in the production and finishing of textiles, as a solubilizer and protective colloid in the preparation and stabilization of polymer dispersions, and as an adhesive raw material.

The present invention relates to novel pyrrolidonyl-containingpolyesters and polyamides, to processes for their preparation, and tothe use of these pyrrolidonyl-containing polyesters and polyamides inspecific industrial areas.

Polyvinylpyrrolidone (PVP) and copolymers of vinyl pyrrolidone preparedby means of free radicals, for example using vinyl acetate, havehitherto found use in various industrial areas. In particular, theirproperties are utilized as complexing agents, film-forming agents, depotformers, enzyme supports, binders and adhesive raw materials. Theapplications are in the cosmetics and pharmaceuticals sectors and in thefoodstuffs, textiles, detergents and not least in the polymers areas,for example as solubilizers or protective colloids.

However, PVP and copolymers thereof have a number of drawbacks in theseapplications, in particular their unsatisfactory biodegradability oreliminability, their toxicity potential (monomeric vinyl pyrrolidone hasbeen classified as carcinogenic in animal experiments) and in some casestheir incompatibility with certain saccharides (for example in mixturesof PVP with maltodextrins). In addition, the applicational properties ofPVP and copolymers thereof are frequently also unsatisfactory.

U.S. Pat. No. 2,993,021 (1) discloses polyesters obtained bypolycondensation of bispyrrolidone derivatives of the structure ##STR2##where R is an alkylene, oxaalkylene, thiaalkylene or azaalkylene bridgehaving 2 to 12 carbon atoms, for example 1,2-ethylene or 1,3-propylene,with a polyhydroxyl compound, for example ethylene glycol or propyleneglycol. These polyesters are suitable, under certain circumstances, asplasticizers for plastics and for the preparation of alkyd resins,which, as is known, play an important role as vehicles in the paintsindustry.

The Israel Journal of Chemistry, Vol. 10 (1972), 949-957 (2) discloseshighly heat-resistant polyamides prepared by reacting aromatic diamines,such as benzidine, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenylether or p-phenylenediamine, with bispyrrolidonedicarboxylic acidsobtained by reacting itaconic acid with said aromatic diamines. Thesepolyamides apparently have low solubility, since they only dissolve inconcentrated sulfuric acid and some partially dissolve indimethylformamide or dimethyl sulfoxide. A suggested use is in adhesiveformulations.

It is an object of the present invention to provide novel materials asreplacement for PVP and copolymers thereof in said areas of applicationwhich do not have the disadvantages of the prior art.

We have found that this object is achieved by pyrrolidonyl-containingpolyesters and polyamides of the formulae I to III ##STR3## where R ishydrogen or C₁ - to C₄ -alkyl, where two radicals R can be linked to oneanother to form a six-membered ring,

X is oxygen or --NR--,

A is C₁ - to C₂₀ -alkylene, which can be interrupted by one or morenon-adjacent oxygen atoms, sulfur atoms or functional groups --NR--,where the nitrogen atom can be protonated or quaternized, --CO--,--CO--O--, --CO--NR--, --SO-- or SO₂ --, and which may carry additionalfunctional groups --COOH or --SO₃ H, C₆ - to C₂₀ -cycloalkylene, C₆ - toC₂₀ -arylene, which may be interrupted by oxygen, sulfur or --NR--,--SO-- or --SO₂ -- and may additionally carry functional groups --COOHor --SO₃ H, or a mixture of such groups,

Z is a group of the formula IV ##STR4## where B is C₁ - to C₂₀-alkylene, which may be interrupted by one or more non-adjacent oxygenatoms, sulfur atoms or functional groups --NR--, where the nitrogen atommay be protonated or quaternized, --CO--, --CO--O--, --CO--O--,--CO--NR--, --SO-- or --SO₂ --, and which may carry additionalfunctional groups --COOH or --SO₃ H, C₆ - to C₂₀ -cycloalkylene or amixture of such groups, or is a mixture of groups of the formula IV withgroups A, and

n is a number from 5 to 500.

C₁ - to C₄ -alkyl R¹ is ethyl, n-propyl, isopropyl, n-butyl, isobutyl,sec-butyl, tert-butyl or, in particular, methyl. If two --NR-- groupsare linked to one another by a C₁ - to C₃ -alkylene group, the tworadicals R can also be linked to one another to form a saturatedsix-membered ring containing two nitrogen atoms, in particular apiperazine ring.

The following are examples of the bridge A and the bridge B (where thelatter cannot contain aromatic rings):

methylene

1,2-ethylene, if desired incorporated into a piperazine ring

1,3-propylene

1,2-propylene

1,4-butylene

2,3-butylene

pentamethylene (for example formed from ε-caprolactam)

hexamethylene

2,5-hexylene

heptamethylene

octamethylene

2,7-octylene

nonamethylene

decamethylene

dodecamethylene

tetradecamethylene

hexadecamethylene

octadecamethylene

eicosamethylene

--CH₂ --O--CH₂

--CH₂ CH₂ --O--CH₂ CH₂ --

--CH₂ CH₂ --O--CH₂ CH₂ --O--CH₂ CH₂ --

--CH₂ CH₂ --O--CH₂ CH₂ --O--CH₂ CH₂ --O--CH₂ CH₂ --

--CH₂ CH₂ CH₂ --O--CH₂ CH₂ --O--CH₂ CH₂ CH₂ --

--CH₂ CH₂ --S--CH₂ CH₂ --

--CH₂ CH₂ CH₂ --S--CH₂ CH₂ CH₂ --

--CH₂ CH₂ CH₂ --S--S--CH₂ CH₂ CH₂ --

--CH₂ CH₂ CH₂ --S--CH₂ CH₂ --S--CH₂ CH₂ CH₂ --

--CH₂ CH₂ --NH--CH₂ CH₂ --

--CH₂ CH₂ --N(CH₃)--CH₂ CH₂ -- ##STR5## --CH₂ CH₂ --NH--CH₂ CH₂--NH--CH₂ CH₂ ----CH₂ CH₂ CH₂ --NH--NH--CH₂ CH₂ CH₂ --

--CH₂ --CO--CH₂ --

--CH₂ --CO--CH₂ CH₂ --

--CH₂ CH₂ --CO--CH₂ CH₂ --

--CH₂ --CO--O--CH₂ --

--CH₂ --CO--O--CH₂ CH₂ --

--CH₂ --CO--NH--CH₂ --

--CH₂ --CO--N(CH₃)--CH₂ --

--(CH₂)₄ --CO--NH--(CH₂)₆ -- (for example formed fromhexamethylenediamine adipate)

--CH₂ --SO--CH₂ --

--CH₂ --SO₂ --CH₂ --

--CH(COOH)--

--CH(CH₂ COOH)--

--CH(CH₂ CH₂ COOH)-- (from glutamic acid)

--CH(SO₃ H)--

--CH(CH₂ SO₃ H)-- ##STR6##

A and B preferably have the following meanings:

1,2-ethylene, if desired incorporated into a piperazine ring

1,3-propylene

1,2-propylene

1,4-butylene

pentamethylene (for example from ε-caprolactam)

hexamethylene

octamethylene ##STR7## --(CH₂)₄ --CO--NH--(CH₂)₆ -- (for example formedfrom hexamethylenediamine adipate)

--CH(CH₂ CH₂ COOH)-- (from glutamic acid) ##STR8##

The bridges A and B in the novel polyesters and polyamides I to III canalso be mixtures of more than one, in particular from 2 to 3, differentgroups of this type. The individual species here are generallydistributed more or less randomly, since the polycondensates I to IIIare in such a case usually prepared by reaction with mixtures of thecorresponding aminoalcohols, diamines or aminocarboxylic acids. If theformulae I to III contain more than one bridge A, the latter can beidentical or different.

Quaternizing agents for tertiary nitrogen atoms in the bridges A and Bcan be, for example, alkyl halides or dialkyl sulfates, such as methylchloride, ethyl chloride, methyl bromide, ethyl bromide, benzylchloride, dimethyl sulfate or diethyl sulfate. --NR-- groups in thebridges A and B can be protonated, in particular, using organic acids,for example lactic acid.

In order to modify the polycondensates II, some, in particular up to 30mol %, of the bispyrrolidone structures IV can, if desired, be replacedby bridges formed from dicarboxylic acids of the formula HOOC--A--COOH.In such a case, preference is given to aromatic dicarboxylic acids,which can also carry sulfo groups in order to increase their watersolubility, for example terephthalic acid, 2-sulfoterephthalic acid,isophthalic acid, 5-sulfoisophthalic acid, phthalic acid, sulfophthalicacids, naphthalenedicarboxylic acids or sulfonaphthalenedicarboxylicacids. The sulfodicarboxylic acids are normally employed as alkali metalor ammonium sulfonates.

The degree of polycondensation n is preferably from 10 to 400, inparticular from 15 to 300. The polyesters and polyamides I to IIIusually have K values of from 5 to 50, in particular from 9 to 40,measured as a 0.1% strength by weight solution in N-methylpyrrolidone.

The present invention also relates to processes for the preparation ofnovel polyesters and polyamides I to III.

Pyrrolidonyl-containing polyesters and polyamides I are expedientlyprepared by reacting itaconic acid, itaconic anhydride, an itaconicester or an itaconyl halide with an aminoalcohol or diamine of theformula HX--A--NH₂ in a molar ratio of approximately 1:1, andpolycondensing the resultant monomeric pyrrolidone derivative atelevated temperature.

Pyrrolidonyl-containing polyamides II are expediently prepared byreacting itaconic acid, itaconic anhydride, an itaconic ester or anitaconyl halide with a diamine of the formula H₂ N--B--NH₂ in a molarratio of approximately 2:1, and polycondensing the resultant monomericbispyrrolidone derivative or a mixture thereof with a dicarboxylic acidor dicarboxylic acid derivative of the formula Y--CO--A--CO--Y, whereeach Y, independently of the others, is OH, O-alkyl, for example O--C₁-- to C₄ -alkyl, or halogen, for example Cl or Br, with a diamine offormula HRN--A--NRH at elevated temperature.

Pyrrolidonyl-containing polyesters and polyamides III are expedientlyprepared by reacting itaconic acid, itaconic anhydride, an itaconicester or an itaconyl halide with an aminocarboxylic acid of the formulaH₂ N--A--CO--Y, where Y is OH, O-alkyl, for example O--C₁ - to C₄-alkyl, or halogen, for example Cl or Br, in a molar ratio ofapproximately 1:1, and polycondensing the resultant monomericpyrrolidone derivative with a diol or diamine of the formula HX--A--XHat elevated temperature.

Suitable starting materials are in particular itaconic acid itself, butalso derivatives thereof, such as its dimethyl or diethyl ester or itsdichloride.

The reaction of itaconic acid or derivatives thereof with monomericcompounds containing primary amino groups to give pyrrolidone structuresis known in principle. The reaction is advantageously carried out underan inert-gas atmosphere, for example under nitrogen, in a solvent,preferably water, and at from about 90° to 120° C.

The subsequent polycondensation reaction in order to produce thepolyesters and polyamides I to III is generally at from 100° to 300° C.,in particular at from 150° to 250° C. Solvent from the first step, forexample water, is expediently removed in advance, for example bydistillation. Water formed during the polycondensation, which is usuallyformed as steam, is likewise expediently removed, either continuouslyduring polycondensation or subsequently thereto. The reaction is carriedout at atmospheric pressure, expediently under an inert-gas atmosphere,or at superatmospheric pressure, for example at up to 25 bar. Thereaction is generally complete within 2 to 10 hours.

The polycondensation reaction can be accelerated by using catalysts inthe conventional amounts for this purpose. Suitable catalysts here arein particular mineral acids or acidic salts of mineral acids, forexample orthophosphoric acid, alkali metal dihydrogenphosphates oralkali metal hydrogensulfates. Heavy-metal salts of fatty acids, such astin octanoate, can also be employed for this purpose. The acidiccatalysts remaining in the product can be neutralized using conventionalbases.

The present invention also relates to pyrrolidonyl-containingpolyurethanes or polyureas and pyrrolidonyl-containing polycarboxylatesobtainable by reacting pyrrolidonyl-containing polyesters or polyamidesof the formulae V to VII ##STR9## where R is hydrogen or C₁ - to C₄-alkyl, where two radicals R can be linked to one another to form asix-membered ring,

X is oxygen or --NR--,

A is C₁ - to C₂₀ -alkylene, which can be interrupted by one or morenon-adjacent oxygen atoms, sulfur atoms or functional groups --NR--,where the nitrogen atom can be protonated or quaternized, --CO--,--CO--O--, --CO--NR--, --SO-- or SO₂ --, and which may carry additionalfunctional groups --COOH or --SO₃ H, C₆ - to C₂₀ -cycloalkylene, C₆ - toC₂₀ -arylene, which may be interrupted by oxygen, sulfur or --NR--,--SO-- or --SO₂ -- and may additionally carry functional groups --COOHor --SO₃ H, or a mixture of such groups,

Z is a group of the formula VIII ##STR10## or a mixture of groups offormula VIII with group A and m is a number from 1 to 50,

with diisocyanates of the formula OCN--D--NCO, where D is C₂ - to C₈-alkylene, C₅ - to C₁₀ -cycloalkylene, phenylene or C₁ - to C₄-alkylphenylene, or dianhydrides of the formula ##STR11## where T is atetravalent radical of a C₂ - to C₆ -alkane, of a C₅ - to C₁₀-cycloalkane, of benzene or of naphthalene.

If the formulae V to VII contain more than one bridge A, the latter maybe identical or different.

The compounds V are expediently prepared by reacting itaconic acid,itaconic anhydride, an itaconic ester or an itaconyl halide with aslight excess of an aminoalcohol or diamine of the formula HX--A--NH₂ orby subsequently adding as excess a small to molar amount of anotheraminoalcohol or diamine HX--A--NH₂ or of a diol of the formula HO--A--OHand allowing this to react, and, if desired, polycondensing the mixtureat elevated temperature to a degree of polycondensation m, so that freeamino or hydroxyl groups which are capable of reacting with diisocyanateor dianhydride are at both ends of the polycondensate chain.

The compounds VI are expediently prepared by reacting itaconic acid,itaconic anhydride, an itaconic ester or an itaconyl halide with anaminoalcohol or diamine of the formula HX--A--NH₂ in a molar ratio ofapproximately 2:1, then reacting the product with a small to molaramount of the same or another aminoalcohol or diamine HX--A--NH₂ or of adiol of the formula HO--A--OH, and, if desired, polycondensing theproduct with the same or another amonoalcohol or diamine HX--A--NH₂ atelevated temperature to the degree of polycondensation m, so that freeamino or hydroxyl groups which are capable of reacting with diisocyanateor dianhydride are at both ends of the polycondensate chain. Some of thebispyrrolidonedicarboxylic acid units can be replaced by dicarboxylicacids of the formula HOOC--A--COOH.

The compounds VII are expediently prepared by reacting itaconic acid,itaconic anhydride, an itaconic ester or an itaconyl halide with anaminocarboxylic acid of the formula H₂ N--A--CO--Y, where Y is OH,O-alkyl, for example O--C₁ - to C₄ -alkyl, or halogen, for example Cl orBr, in a molar ratio of approximately 1:1, then reacting the productwith a small to molar amount of an aminoalcohol or diamine of theformula HX--A--NH₂ or of a diol of the formula HO--A--OH, and, ifdesired, polycondensing the product with the same or anotheraminoalcohol or diamine HX--A--NH₂ at elevated temperature to the degreeof polycondensation m, so that the amino or hydroxyl groups which arecapable of reacting with diisocyanate or dianhydride are at both ends ofthe polycondensation chain.

Suitable diisocyanates OCN--D--NCO are C₂ - to C₈ -alkylenediisocyanates, for example 1,2-ethylene diisocyanate, 1,4-butylenediisocyanate, hexamethylene diisocyanate or octamethylene diisocyanate,C₅ - to C₁₀ -cycloalkylene diisocyanates, for example 1,3-cyclopentylenediisocyanate, 1,3- or 1,4-cyclohexylene diisocyanate or isophoronediisocyanate, o-, m- or p-phenylene diisocyanate or (C₁ - to C₄-alkyl)phenylene diisocyanates, for example tolylene diisocyanate.

The tetravalent radical T in the dianhydrides used is, for example,1,1,2,2-substituted ethane, 1,2,3,4-substituted butane, 1,2,3,4- or1,2,4,5-substituted cyclohexane, 1,2,3,4- or 1,2,4,5-substituted benzeneor 1,2,3,4- or 2,3,6,7-substituted naphthalene.

The reaction to give the novel pyrrolidonyl-containing polyurethanes orpolyureas and the novel pyrrolidonyl-containing polycarboxylates iscarried out by methods known per se and therefore requires no furtherexplanation.

The novel pyrrolidonyl-containing polyurethanes and polyureas and thenovel pyrrolidonyl-containing polycarboxylates are in principle suitablefor the same applications as the novel pyrrolidonyl-containingpolyesters and polyamides of the formulae I to III described above.

The present invention furthermore relates to the use ofpyrrolidonyl-containing polyesters and polyamides containing at leastone structural unit of the formula IX ##STR12## where X is oxygen or--NR--,

R is hydrogen or C₁ - to C₄ -alkyl, where two radicals R can be linkedto one another to form a six-membered ring,

A is C₁ - to C₂₀ -alkylene, which can be interrupted by one or morenon-adjacent oxygen atoms, sulfur atoms or functional groups --NR--,where the nitrogen atom can be protonated or quaternized, --CO--,--CO--O--, --CO--NR--, --SO-- or --SO₂ --, and which may carryadditional functional groups --COOH or --SO₃ H, C₆ - to C₂₀-cycloalkylene, C₆ - to C₂₀ -arylene, which may be interrupted byoxygen, sulfur or --NR--, --SO-- or --SO₂ -- and may additionally carryfunctional groups --COOH or --SO₃ H, or a mixture of such groups,

as film-forming agents and conditioners in hair cosmetic formulations.

Preferred pyrrolidonyl-containing polyesters and polyamides are those ofthe formulae I to III, where --NR-- in the formula II can also bereplaced by oxygen, and the products of the reaction of compounds of theformulae V to VII with diisocyanates of the formula OCN--D--NCO ordianhydrides of the formula ##STR13##

The pyrrolidonyl-containing polyesters and polyamides described haveexcellent applicational properties as film-forming agents in hairsprays, hair foams, hair-setting compositions or hair gels and asconditioners in hair-care rinses or hair shampoos. They are generallyreadily water- or alcohol-soluble, and their viscosity is significantlylower than that of comparable known compositions.

The present invention furthermore relates to the use ofpyrrolidonyl-containing polyesters and polyamides containing at leastone structural unit IX for stabilizing hydrogen peroxide in aqueoussolution.

Accordingly, the present invention also relates to complexes of hydrogenperoxide and these pyrrolidonyl-containing polyesters or polyamideswhich preferably contain from 0.5 to 35% by weight, in particular from 5to 18% by weight, of H₂ O₂.

Preferred pyrrolidonyl-containing polyesters and polyamides here arethose of the formulae I to III, where --NR-- in the formula II can alsobe replaced by oxygen, and the products of the reaction of the compoundsof the formulae V to VII with diisocyanates of the formula OCN--D--NCOor dianhydrides of the formula ##STR14##

Said hydrogen peroxide/polyester and polyamide complexes have asignificantly improved stabilization behavior in aqueous solution thandoes PVP, in particular in the temperature range from 60° to 90° C.While a decomposition of approx. 20% has been observed for 0.2% byweight technical-grade hydrogen peroxide over 9 hours at 80° C., thisfigure is approx. at 8% for PVP and about 2% for the polyamides orpolyesters described. In addition, the stabilization is successful ifdecomposition of the hydrogen peroxide at elevated temperature isadditionally accelerated by relatively high pH values. At pH 9 (60° C.,6 ppm of copper ions), 99.4% of the initial hydrogen peroxide hasdecomposed after 45 minutes, whereas, under the same conditions, only30% of the hydrogen peroxide has decomposed with the polyamides orpolyesters described, but 58% with PVP.

Solid polycondensate/hydrogen peroxide complexes containing 33% byweight of hydrogen peroxide, based on the total solids content, can alsobe prepared from the solutions. The stabilizing effect is achieved evenif only small amounts (from 1 to 30%) of the pyrrolidone units areintroduced into a polyamide or a polyester. Solutions of the polyamideor polyester and hydrogen peroxide, preferably in water, are evaporatedto dryness or solid polyamide or polyester is sprayed with a hydrogenperoxide solution in a fluidized-bed process and subsequently dried. Thedecomposition amounts to 25% over 10 hours at 50° C., while 40% of aconventional urea/hydrogen peroxide complex decomposes under the sameconditions.

The hydrogen peroxide complexes described can be used, for example, intoothpastes, in acne therapy, in disinfectants, in wound dressings, inhair cosmetics (hair coloring) or as the solid component for chemicalreactions, such as polymerizations or oxidations.

The present invention furthermore relates to the use ofpyrrolidonyl-containing polyesters and polyamides containing at leastone structural unit IX for complexing iodine.

Accordingly, the present invention relates to complexes of iodine andthese pyrrolidonyl-containing polyesters and polyamides which preferablycontain from 2 to 20% by weight, in particular from 5 to 14% by weight,especially from 6 to 12% by weight, of iodine.

Preferred pyrrolidonyl-containing polyesters and polyamides here arethose of the formulae I to III, where --NR-- in the formula II can alsobe replaced by oxygen, and the products of the reaction of the compoundsof the formulae V to VII with diisocyanates of the formula OCN--D--NCOor dianhydrides of the formula ##STR15##

Polymer/iodine complexes of this type are particularly suitable as finedisinfectants in the medical sector. The novel complexes of iodine and,if desired, iodides, such as potassium iodide, and other oxidants andthe pyrrolidonyl-containing polyesters and polyamides described are atleast equal to the known PVP/iodine complexes in their applicationproperties.

The present invention furthermore relates to the use ofpyrrolidonyl-containing polyesters and polyamides containing at leastone structural unit IX as tablet binders and as a constituent of filmcoatings in pharmaceutical preparations.

Preferred pyrrolidonyl-containing polyesters and polyamides here arethose of the formulae I to III, where --NR-- in the formula II can alsobe replaced by oxygen, and the products of the reaction of the compoundsof the formulae V to VII with diisocyanates of the formula OCN--D--NCOor dianhydrides of the formula ##STR16##

The present invention furthermore relates to the use ofpyrrolidonyl-containing polyesters and polyamides containing at leastone structural unit IX for enzyme stabilization and for bleachstabilization in detergent formulations.

Preferred pyrrolidonyl-containing polyesters and polyamides here arethose of the formulae I to III, where --NR-- in the formula II can alsobe replaced by oxygen, and the products of the reaction of the compoundsof the formulae V to VII with diisocyanates of the formula OCN--D--NCOor dianhydrides of the formula ##STR17##

The present invention furthermore relates to the use ofpyrrolidonyl-containing polyesters and polyamides containing at leastone structural unit IX as auxiliaries in the production and finishing oftextiles.

Preferred pyrrolidonyl-containing polyesters and polyamides here arethose of the formulae I to III, where --NR-- in the formula II can alsobe replaced by oxygen, and the products of the reaction of the compoundsof the formulae V to VII with diisocyanates of the formula OCN--D--NCOor dianhydrides of the formula ##STR18##

The present invention furthermore relates to the use ofpyrrolidonyl-containing polyesters and polyamides containing at leastone structural unit IX as solubilizers and protective colloids in thepreparation and stabilization of polymer dispersions.

Preferred pyrrolidonyl-containing polyesters and polyamides here arethose of the formulae I to III, where --NR-- in the formula II can alsobe replaced by oxygen, and the products of the reaction of the compoundsof the formulae V to VII with diisocyanates of the formula OCN--D--NCOor dianhydrides of the formula ##STR19##

The present invention furthermore relates to the use ofpyrrolidonyl-containing polyesters and polyamides containing at leastone structural unit of the formula X ##STR20## where X is oxygen or--NR--,

R is hydrogen or C₁ - to C₄ -alkyl, where two radicals R can be linkedto one another to form a six-membered ring, and

B is C₁ - to C₂₀ -alkylene, which can be interrupted by one or morenon-adjacent oxygen atoms, sulfur atoms or functional groups --NR--where the nitrogen atom can be protonated or quaternized, --CO--,--CO--O--, --CO--NR--, --SO-- or --SO₂ --, and may carry additionalfunctional groups --COOH or --SO₃ H, C₆ - to C₂₀ -cycloalkylene or amixture of such groups,

as adhesives.

Preferred pyrrolidonyl-containing polyesters and polyamides here arethose of the formulae I to III, where --NR-- in the formula II can alsobe replaced by oxygen, and the products of the reaction of the compoundsof the formulae V to VII with diisocyanates of the formula OCN--D--NCOor dianhydrides of the formula ##STR21##

The pyrrolidonyl-containing polyesters and polyamides described, inparticular those of the formulae I to III and the products of thereaction of the compounds V to VII with diisocyanates or dianhydrides,have good biodegradability or eliminability since the polymer backbonecontains groups which can be readily removed hydrolytically.

The polycondensates described are easy to prepare, and, for example, noorganic solvents are needed for their preparation. The starting compounditaconic acid is readily and inexpensively obtainable from sugars ormolasses by fermentative processes.

In many applications, the polycondensates described are superior to PVPand copolymers thereof.

PREPARATION EXAMPLES General Preparation Procedure A

The monomeric pyrrolidone derivative conforming to the formula I isprepared in a known manner from itaconic acid and the aminoalcohol ordiamine shown in Table 1 or a mixture of these reactants in water assolvents at approx. 100° C. under a nitrogen atmosphere. Virtually allthe water is subsequently removed by distillation, and thepolycondensation is effected by heating to approx. 250° C. underatmospheric pressure under a nitrogen atmosphere. Water of condensationformed as steam is continuously removed by passing a stream of nitrogenthrough the mixture. The reaction is complete after about 6 to 15 hours.The use of a catalyst, such as orthophosphoric acid or sodium dihydrogenphosphate in conventional amounts, reduces the reaction time to fromabout 3 to 10 hours.

General Preparation Procedure B

The bispyrrolidonedicarboxylic acid of the formula XI ##STR22## isprepared in a known manner from itaconic acid and ethylenediamine in amolar ratio of 2:1 in water as solvent at approx. 100° C. under anitrogen atmosphere. Virtually all the water is subsequently removed bydistillation, the diamine or mixture of diamines shown in Table 1 andany dicarboxylic acids or aminocarboxylic acids shown in Table 1 areadded, and the polycondensation is effected by heating to approx. 250°C. under atmospheric pressure under a nitrogen atmosphere. Water ofcondensation formed as steam is continuously removed by passing a streamof nitrogen through the mixture. The reaction is complete after fromabout 6 to 15 hours. The use of a catalyst, such as orthophosphoric acidor sodium dihydrogen phosphate in the conventional amount, reduces thereaction time to from about 3 to 10 hours.

                                      TABLE 1    __________________________________________________________________________    Composition  molar amount! and K values of the polycondensates prepared                Pyrrolidonyl-            K value          Preparation                supplying                      Aminoalcohol/                             Aminocar-                                   Dicarboxylic                                         (0.1% by wt.    Example No.          procedure                compound                      diamine                             boxylic acid                                   acid  in NMP)    __________________________________________________________________________    1     A     IA  1!                      EA  1! --    --     9.6    2     A     IA  1!                      EDA  4!                             --    --    33.0    3     A     IA  1!                      AEP  1!                             --    --    24.1    4     B     XI  1!                      EDA  1!                             --    --    31.3    5     B     XI  1!                      EDA  0.5!,                             --    --    32.2                      P  0.5!    6     B     XI  1!                      EDA  0.8!,                             GA  0.3!                                   --    29.2                      AEP  0.2!    7     A     IA  1!                      EDA  0.5!,                             --    --    29.9                      DC  0.5!    8     B     XI  1!                      EDA  0.3!,                             --    --    31.7                      DC  0.7!    9     B     XI  1.2!                      EDA- 0.3!,                             GA  0.3!                                   --    22.1                      DC  1.1!    10    B     XI  1!                      DAP  0.5!,                             AH  0.3!                                   --    29.2                      DC  0.5!    11    B     XI  1!                      DAP  0.3!,                             --    IPA  0.4!                                         22.8                      DC  1!                      AEP  0.2!    12    B     XI  1!                      EDA  0.15!,                             --    SIPA  0.1!                                         24.3                      DC  1!,    __________________________________________________________________________     IA = itaconic acid     XI = bispyrrolidonedicarboxylic acid of the formula XI     EA = ethanolamine     EDA = ethylenediamine     AEP = N(2-aminoethyl)piperazine     P = piperazine     DC = 4,4diaminodicyclohexylmethane (dicyhane)     DAP = 1,2diaminopropane     GA = glutamic acid     AH = AH salt (hexamethylenediamine adipate)     IPA = isophthalic acid     SIPA = 5sulfoisophthalic acid     NMP = Nmethylpyrrolidone

EXAMPLE 13 Preparation of a Pyrrolidonyl-Containing Polyurea

160 g (0.1 mol) of a poly(itaconic acid ethylenediamine) prepared usinga slight excess of ethylenediamine were dissolved with stirring at 20°C. in 375 g of a mixture of ethanol and water in a ratio by volume of4:1. 15.14 g (0.09 mol) of hexamethylene diisocyanate were then addeddropwise, with the internal temperature remaining below 30° C. Thereaction solution was then stirred at 20° C. for a further 2 hours. Thesolvent was removed at 70° C. in a vacuum drying cabinet. Drying gave awater-soluble, hard solid. Instead of drying, an aqueous solution of theproduct was obtainable by adding further water and removing the ethanolby distillation at about 60° C. under slightly reduced pressure.

Application properties in hair cosmetics

The polycondensates from Examples 1 to 6 were investigated for theirsuitability as hair conditioners. To this end, their solubilities inethanol and water, their surfactant compatibility and their combabilityfrom the hair were determined. The latter determination was carried outusing a hair-care rinse of commercial composition containing thepolycondensates from Examples 1 to 6.

                                      TABLE 2    __________________________________________________________________________    Solubilities, surfactant compatibility and combability of the    polycondensates from Examples 1 to 6            Solubility (5% strength            by wt.) in                Ethanol/    Example     water   Surfactant                               Combability    No.     Ethanol                (1:1)                    Water                        compatibility                               wet  dry    __________________________________________________________________________    1       0   +   +   good   very good                                    very good    2       0   +   +   good   very good                                    very good    3       0   +   +   good   good very good    4       0   +   +   good   very good                                    very good    5       0   +   0   good   very good                                    very good    6       0   +   +   good   very good                                    very good    for comparison:    PVP-QVI +   +   0   good   good good    __________________________________________________________________________     + = soluble,     0 = cloudy

In the comparative example, PVP-QVI is a commercially available haircosmetic polymer made from N-vinylpyrrolidone and vinylimidazoliummethochloride.

The surfactant compatibility was determined in 5% strength by weightaqueous solution containing 14% by weight of a commercially availablefatty alcohol ether sulfate (Texapon® NSO).

The polycondensates from Examples 7 to 12 were investigated for theirsuitability as film formers in hair spray and hair-setting formulations.To this end, their solubilities in ethanol and water, the tack and easeof washing out of a film on a glass plate and the curl retention andflexural rigidity of treated hairs were determined.

For the measurement of curl retention and flexural rigidity, an aerosolhair spray formulation having the following composition was employed:

3% by weight of the polycondensate from Examples 7 to 12

52% by weight of ethanol

10% by weight of distilled water

35% by weight of dimethyl ether.

For the production of a film on a glass plate, a formulation having thefollowing composition was employed:

4% by weight of the polycondensate from Examples 7 to 12

32% by weight of ethanol

64% by weight of distilled water.

                                      TABLE 3    __________________________________________________________________________    Solubilities, tack, ease of washing out, curl retention and    flexural rigidity of the polycondensates from Examples 7 to 12    Solubility (5 %    Film on Hair    strength by weight) in                       glass plate                               treatment              Ethanol/     Ease of                               Curl Flexural    Ex.       water    Tack                           washing                               retention                                    rigidity    No.  Ethanol              (1:1)                  Water                        score!                           out  %!   g!    __________________________________________________________________________     7   D    +   0    4   good                               17   312     8   +    +   0    3   still                               23   230                           good     9   0    +   0    3   good                               37   215    10   +    +   0    1   good                               18   55    11   0    +   0    1   good                               41   82    12   0    +   D    1   good                               29   61    for    comp.:    PVP-PVA         +    +   0    5   good                               35   79    __________________________________________________________________________     + = soluble,     0 = cloudy,     D = dispersion

In the comparative example, PVP-PVA was a commercially availablehair-cosmetic polymer comprising 30% by weight of N-vinylpyrrolidone and70% by weight of vinyl acetate.

In the assessment of tack, 1 (non-tacky) denotes the best score and 5(tacky) the worst score for hair-cosmetic polymers.

We claim:
 1. A pyrrolidonyl-containing polyester or polyamide of theformula III ##STR23## where X is oxygen or --NR--,R is hydrogen, C₁ - toC₄ -alkyl, or two radicals R are linked to one another to form asix-membered ring, A is a C₁ - to C₂₀ -alkylenewhich is optionallyinterrupted by one or more non-adjacentoxygen atoms, sulfur atoms, orfunctional groups --NR-- where the nitrogen atom is optionallyprotonated or quarternized, --CO--, --CO--O--, --CO--NR--, --SO--, or--SO₂ --, and which optionally carries functional groups --COOH or --SO₃H, C₆ - to C₂₀ -cycloalkylene, C₆ - to C₂₀ -arylene which is optionallyinterrupted by oxygen, sulfur, --NR--, --SO--, or --SO₂ -- andoptionally substituted by --COOH or --SO₃ H, or a mixture of suchgroups, and n is a number from 5 to
 500. 2. The pyrrolidonyl-containingpolyester or polyamide of claim 1 wherein A is 1,2-ethylene,1,2-ethylene incorporated into a piperazine ring, 1,3-propylene,1,2-propylene, 1,4-butylene, pentamethylene, hexamethylene,octamethylene, ##STR24##
 3. A pyrrolidonyl-containing polyester orpolyamide containing at least one structural unit of the formula##STR25## where X is oxygen or --NR--,R is hydrogen, C₁ - to C₄ -alkyl,or two radicals R are linked to one another to form a six-membered ring,and A is a C₁ - to C₂₀ -alkylene,which is optionally interrupted by oneor more non-adjacent oxygen atoms,sulfur atoms, or functional groups--NR--, where the nitrogen atom is optionally protonated orquarternized, --CO--, --CO--O--, --CO--NR--, --SO-- or --SO₂ --, andwhich optionally carries functional groups --COOH or --SO₃ H, C₆ - toC₂₀ -cycloalkylene, C₆ - to C₂₀ -arylene which is optionally interruptedby oxygen, sulfur, --NR--, --SO--, or --SO₂ -- and optionally carriesfunctional groups --COOH or --SO₃ H, or a mixture of such groups.
 4. Apyrrolidonyl-containing polyurethane or polyurea or apyrrolidonyl-containing polycarboxylate obtained by reacting(1) apyrrolidonyl-containing polyester or polyamide of the formulae V to VII##STR26## where R is hydrogen, C₁ - to C₄ -alkyl, or two radicals R arelinked to one another to form a six-membered ring, X is oxygen or--NR--, A is a C₁ - to C₂₀ -alkylene,which is optionally interrupted byone or more non-adjacentoxygen atoms, sulfur atoms, or functional groups--NR-- where the nitrogen atom is optionally protonated or quarternized,--CO--, --CO--O--, --CO--NR--, --SO--, or --SO₂ --, and which optionallycarries functional groups --COOH or --SO₃ H, C₆ - to C₂₀ -cycloalkylene,C₆ - to C₂₀ -arylene which is optionally interrupted by oxygen, sulfur,--NR--, --SO--, or --SO₂ -- and optionally carries --COOH or --SO₃ H, ora mixture of such groups, and Z is a group of the formula VIII ##STR27##or a mixture of groups of formula VIII with group A and m is a numberfrom 1 to 50,with (2) diisocyanates of the formula OCN--D--NCO, where Dis C₂ - to C₈ -alkylene, C₅ - to C₁₀ -cycloalkylene, phenylene, or C₁ -to C₄ -alkylphenylene, or dianhydrides of the formula ##STR28## where Tis a tetravalent radical of a C₂ - to C₆ -alkane, of a C₅ - to C₁₀-cycloalkane, of benzene, or of naphthalene.
 5. An adhesive compositioncomprising a pyrrolidonyl-containing polyester or polyamide containingat least one structural unit of the formula ##STR29## where X is oxygenor --NR--,R is hydrogen, C₁ - to C₄ -alkyl, or two radicals R are linkedto one another to form a six-membered ring, and A is a C₁ - to C₂₀-alkylene,which is optionally interrupted by one or morenon-adjacentoxygen atoms, sulfur atoms, or functional groups --NR--,where the nitrogen atom is optionally protonated or quarternized,--CO--, --CO--O--, --CO--NR--, --SO--, or --SO₂ --, which optionallycarries functional groups --COOH or --SO₃ H, C₆ - to C₂₀ -cycloalkylene,C₆ - to C₂₀ -arylene, which is optionally interrupted by oxygen, sulfur,--NR--, --SO--, or --SO₂ -- and optionally carries functional groups--COOH or --SO₃ H, or a mixture of such groups, and B is C₁ - to C₂₀-alkylene, which is optionally interrupted by one or morenon-adjacentoxygen atoms, sulfur atoms, or functional groups --NR--,where the nitrogen atom is optionally protonated or quarternized,--CO--, --CO--O--, --CO--NR--, --SO--, or --SO₂ --, and which optionallycarries functional groups --COOH or --SO₃ H, C₆ - to C₂₀ -cycloalkylene,or a mixture of such groups.
 6. A process for the preparation of apyrrolidonyl-containing polyester or polyamide III as defined in claim1, which comprisesreacting itaconic acid, itaconic anhydride, anitaconic esters or an itaconyl halide with an aminocarboxylic acid ofthe formula H₂ N--A--CO--Y, where Y is OH, O-alkyl or halogen, in amolar ratio of approximately 1:1, and polycondensing the resultantmonomeric pyrrolidone derivative with a diol or diamine of the formulaHX--A--XH at elevated temperature.
 7. A stabilized aqueous solution ofhydrogen peroxide comprising a pyrrolidonyl-containing polyester orpolyamide as defined in claim 3 as stabilizing agent.
 8. A complex ofhydrogen peroxide and a pyrrolidonyl-containing polyester or polyamideas claimed in claim
 3. 9. A complex of iodine and apyrrolidonyl-containing polyester or polyamide as claimed in claim 3.10. A pharmaceutical preparation comprising a pyrrolidonyl-containingpolyester or polyamide as defined in claim 3 as tablet binder or as aconstituent of film coatings.
 11. A stabilized detergent formulationcomprising a pyrrolidonyl-containing polyester or polyamide as definedin claim 3 for enzyme stabilization or for bleach stabilization.
 12. Atextile comprising a pyrrolidonyl-containing polyester or polyamide asdefined in claim 3 as an auxiliary in the production and finishing. 13.A polymer dispersion comprising a pyrrolidonyl-containing polyester orpolyamide as defined in claim 3 as a solubilizer or protective colloidin the preparation and stabilization.
 14. A hair cosmetic formulationcomprising as a film-forming agent and conditioner apyrrolidonyl-containing polyester or polyamide containing at least onestructural unit of the formula as set forth in claim
 3. 15. Apyrrolidonyl-containing polyurethane or polyurea or apyrrolidonyl-containing polycarboxylate obtained by reacting apyrrolidonyl-containing polyester or polyamide of the formula VII ofclaim 4 with diisocyanates of the formula OCN--D--NCO, where D is C₂ -C₈ -alkylene, C₅ - to C₁₀ -cycloalkylene, phenylene or C₁ - to C₄-alkylphenylene, or dianhydrides of the formula ##STR30## where T is atetravalent radical of a C₂ - to C₆ -alkane, of a C₅ - to C₁₀-cycloalkane, of benzene, or of naphthalene.